EP3027298B1 - Membrankaskade mit sinkender trenntemperatur - Google Patents

Membrankaskade mit sinkender trenntemperatur Download PDF

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Publication number
EP3027298B1
EP3027298B1 EP14744819.5A EP14744819A EP3027298B1 EP 3027298 B1 EP3027298 B1 EP 3027298B1 EP 14744819 A EP14744819 A EP 14744819A EP 3027298 B1 EP3027298 B1 EP 3027298B1
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Prior art keywords
stage
membrane
cascade
separation
reaction
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German (de)
English (en)
French (fr)
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EP3027298A1 (de
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Markus Priske
Robert Franke
Bart Hamers
Patrick Schmidt
Andrzej GÓRAK
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Evonik Operations GmbH
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Evonik Oxeno GmbH and Co KG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/12—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/08—Specific process operations in the concentrate stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/10—Temperature control
    • B01D2311/106—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
    • B01D2311/251—Recirculation of permeate
    • B01D2311/2512—Recirculation of permeate to feed side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/025—Permeate series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/027—Christmas tree arrangements

Definitions

  • the invention relates to a method for separating a mixture of substances by means of a membrane cascade having at least two stages, in which in each stage a substance separation takes place on at least one membrane at a separation temperature assigned to the respective stage.
  • a separation operation to be a measure for the qualitative separation of mixtures of substances, in which an input mixture of substances containing several components is converted into at least two output mixtures of substances, whereby the resulting output mixtures have a different quantitative composition than the input mixture.
  • the resulting output mixtures usually have a particularly high concentration of the desired component; in the best case, they are pure products.
  • the degree of purification or the separation sharpness is usually in conflict with the throughput and the required equipment and energy consumption.
  • the substance mixture 0 to be separated is fed as feed F to a membrane 1, which has a different permeability for the components contained in the substance mixture 0.
  • Components that pass through the membrane 1 particularly well are collected and discharged as permeate P beyond the membrane 1.
  • Components that the membrane 1 preferentially retains are collected and discharged on this side of the membrane 1 as retentate R.
  • membrane separation processes over other separation processes is the low energy requirement. Usually only mechanical power is required to operate pumps to maintain the required flows and pressures. Unlike thermal separation processes, membrane separation processes do not require thermal energy.
  • a specific disadvantage of membrane separation processes is that this relatively new technology depends on the availability of membranes.
  • the effective separation of specific components from the mixture of substances often requires a special membrane material, which is not always available in sufficient quantities or is not even known.
  • the separation of large-volume material flows however, requires very large membrane surfaces and, as a result, a correspondingly large amount of material and high investment costs.
  • the rejection is a measure of the ability of a membrane to enrich a component contained in the feed in the retentate or to deplete it in the permeate.
  • the concentrations x P and x R are to be measured directly on both sides of the membrane.
  • the membrane has a low rejection rate for the component to be retained - for example because no more effective membrane material is known - the material stream to be separated must be fed to the membrane several times in order to achieve sufficient rejection overall. This is done either by returning the permeate to the feed of the same membrane or by feeding a second membrane with the permeate from the first membrane.
  • a membrane separation process in which the material flow to be separated permeates through several membranes is called multi-stage.
  • Multi-stage membrane separation processes are carried out in so-called membrane cascades; these are arrangements of several individual membranes that are connected in series and/or parallel.
  • Membrane cascades usually also include pumps to maintain the transmembrane pressure required as a driving force across the membrane, as well as any return lines that conduct partial flows within the cascade multiple times through individual stages.
  • each membrane cascade can be viewed as a black box like a single membrane, which has the Figure 1 shown basic connections feed, retentate and permeate.
  • Figure 1 shows basic connections feed, retentate and permeate.
  • membranes can be connected in parallel and/or in series within a membrane cascade. This happens quite frequently in technology, since membranes are usually technically designed as a membrane module with a limited membrane area and the required total area is provided by means of several membrane modules connected in parallel.
  • a stage is a separation step in which a pressure drop occurs at one or more membranes. This pressure drop is the difference between feed and permeate at the membrane in question and is called the transmembrane pressure. Without this pressure drop, no separation takes place at the membrane. Since in a multi-stage membrane process the pressure loss that occurred after the first stage must be rebuilt, the number of stages can also be read off from the number of pumps for setting or restoring the transmembrane pressure. Alternatively, although rarely implemented in practice, the transmembrane pressure difference of two or more stages can also be generated by a pump. To do this, the pump upstream of a stage generates the total transmembrane pressure of two or more stages. This means that the permeate pressure of the upstream stage forms the feed pressure of the downstream stage.
  • the amplifier cascade 10 can be understood as a black box which, like a single membrane, receives the mixture of substances 0 to be separated as feed F and separates it into a resulting retentate R and a resulting permeate P.
  • the amplifier cascade 10 comprises two stages 11, 12 connected in series in the direction of the permeate flow, which in turn form a or comprise several membranes.
  • the incoming feed F is conveyed by a feed pump 13 to the first stage 11. There, a first separation of substances takes place on a membrane, so that a retentate from the first stage 14 and a permeate from the first stage 15 are obtained.
  • the retentate from the first stage 14 corresponds to the resulting retentate R from the amplifier cascade 10 and is discharged from the separation process.
  • the permeate 15 of the first stage 11 is fed as feed to the second stage 12.
  • a high-pressure pump 16 is provided between the first and second stages.
  • the retentate 17 of the second stage 12 is recycled into the feed of the first stage 11 to be purified again.
  • amplification cascades serve to enrich a component contained in the incoming material stream 0 and preferentially passed through by the membranes in the resulting permeate P.
  • a stripping cascade is used.
  • the stripping cascade 20 is in turn to be regarded as a black box corresponding to a single membrane which is supplied with the incoming material stream 0 as feed F, which separates the feed F into a resulting retentate R and a resulting permeate P.
  • the output cascade 20 differs from that in Figure 2
  • the amplifier cascade 10 shown in the figure is characterized by the fact that the stages are arranged one after the other in the direction of the retentate flow.
  • Figure 3 The two-stage output cascade shown has two stages 21, 22.
  • the material stream 0 In order to separate the material stream 0, it is fed into the first stage 21 of the stripping cascade 20 and separated there into permeate 24 and retentate 25.
  • a pressure booster pump 23 is provided to generate the necessary transmembrane pressure.
  • the permeate 25 of the first stage 21 is discharged from the stripping cascade 20 and thus corresponds to the resulting permeate P.
  • the retentate 24 of the first stage 21 is fed as feed to the second stage 22.
  • no pump arranged between the first stage 21 and the second stage 22 is required, since the transmembrane pressure always drops in the direction of the permeate, so that the pressure of the retentate 24 - apart from flow losses - essentially corresponds to that of the feed of the first stage 21.
  • the permeate 26 of the second stage 22 is recycled and mixed with the feed of the first stage 21.
  • the booster pump 23 compensates for the pressure loss of the permeate 26 suffered in the second stage 22.
  • Membrane cascades are already widely used in the fields of water desalination, gas separation and pharmaceutical purification.
  • a catalytic reaction we mean a chemical reaction in which at least one reactant is converted into at least one product in the presence of a catalyst.
  • the reactant and product are jointly referred to as reactants.
  • the catalyst is essentially not consumed during the reaction; apart from the usual aging and decomposition phenomena.
  • the reaction is carried out in a locally limited reaction zone.
  • this is a reactor of any design, but it can also be a number of reactors connected to one another.
  • the material removed continuously or discontinuously from the reaction zone is referred to here as the reaction mixture.
  • the reaction mixture comprises at least the target product of the reaction. Depending on the technical reaction procedure, it can also contain unreacted reactants, more or less desired secondary or accompanying products from subsequent or side reactions and solvents. In addition, the reaction mixture can also comprise the catalyst.
  • Catalytically performed chemical reactions can be divided into two groups with regard to the phase state of the catalyst used: Firstly, there are heterogeneously catalyzed reactions, in which the catalyst is present as a solid in the reaction zone and is surrounded by reactants. In homogeneous catalysis, however, the catalyst is dissolved in the reaction mixture. Homogeneously dissolved catalysts are usually significantly more catalytically effective than heterogeneous catalysts.
  • the separation of the catalyst is technically simple in heterogeneously catalyzed reactions: the solid catalyst simply remains in the reaction zone while the liquid and/or gaseous reaction mixture is withdrawn from the reactor. The separation of the heterogeneous catalyst from the reaction mixture thus takes place mechanically and directly within the reaction zone.
  • This task is particularly relevant in the field of rhodium-catalyzed hydroformylation.
  • Hydroformylation - also known as the oxo reaction - makes it possible to convert olefins (alkenes) into aldehydes using synthesis gas (a mixture of carbon monoxide and hydrogen).
  • synthesis gas a mixture of carbon monoxide and hydrogen
  • the resulting aldehydes then have one more carbon atom than the olefins used.
  • Subsequent hydrogenation of the aldehydes produces alcohols, which are also called "oxo alcohols" due to their origin.
  • olefins used as substrates in hydroformylation are those that have two to 20 carbon atoms. Since the alcohols obtainable through hydroformylation and hydrogenation can be used in a variety of ways - for example as plasticizers for PVC, as detergents in washing agents and as fragrances - hydroformylation is practiced on a large industrial scale.
  • Either cobalt or rhodium-based catalyst systems are used industrially, with the latter being complexed with an organophosphorus compound as a ligand.
  • Phosphine, phosphite or phosphoramidite compounds are usually used as ligands.
  • These catalyst systems are all present as homogeneous catalysts dissolved in the reaction mixture.
  • the hydroformylation reaction is usually carried out in two phases, with a liquid phase containing the olefins, the dissolved catalyst and the products, and a gas phase which is essentially formed by synthesis gas.
  • the valuable products are then either withdrawn from the reactor in liquid form ("liquid recycle”) or discharged in gaseous form with the synthesis gas ("gas recycle”).
  • liquid recycle liquid form
  • gas recycle gas recycle
  • a special case is the Ruhrchemie/Rhöne-Poulenc process, in which the catalyst is in an aqueous phase.
  • hydroformylation processes are also carried out in the presence of a solvent, for example alkanes contained in the feed mixture.
  • a solvent for example alkanes contained in the feed mixture.
  • Rh-based, homogeneously catalyzed hydroformylations is the mastery of catalyst separation.
  • Rh is a very expensive precious metal, the loss of which must be avoided at all costs. For this reason, the rhodium must be separated and recovered as completely as possible from the product stream. Since the Rh concentration in typical hydroformylation reactions is only 20 to 100 ppm and a typical "world scale" oxo plant achieves an annual output of 200,000 tons, separation equipment must be used that allows a high throughput on the one hand and reliably separates the Rh, which is only contained in small quantities, on the other. To make matters worse, the catalyst complexes used react sensitively to parameter changes (e.g. temperature changes and/or changes in the CO partial pressure in the reaction mixture). If such a change occurs, the catalyst complex can be deactivated, which in the worst case is irreversible.
  • parameter changes e.g. temperature changes and/or changes in the CO partial pressure in the reaction mixture
  • the phosphorus-organic compounds that can be part of the catalyst complexes as ligands are also not stable indefinitely. They can be decomposed by moisture, oxygen or excessively high temperatures, for example, which also results in deactivation of the catalyst. A deactivated catalyst can only be reactivated with great effort at best. The catalyst must therefore be separated particularly gently. Another important development goal is the energy efficiency of the separation operations.
  • Membrane separation technology is suitable for the separation of homogeneous catalyst systems because it consumes less thermal energy and is able to protect the catalyst: Report on the possibilities of using membrane technology for the processing of hydroformylation mixtures Priske, M. et al.: Reaction integrated separation of homogeneous catalysts in the hydroformylation of higher olefins by means of organophilic nanofiltration. Journal of Membrane Science, Volume 360, Issues 1-2, 15 September 2010, Pages 77-83; doi:10.1016/j.memsci.2010.05.002 .
  • a membrane-supported separation of homogeneous catalyst from hydroformylation mixtures is also described in the previously unpublished German patent application EN 10 2012 223 572 A1 described. Although several nanofiltrations are planned within one system, the individual nanofiltrations are each assigned to a reactor in a reactor cascade. The nanofiltrations themselves do not form a membrane cascade.
  • the invention is therefore based on the object of specifying a membrane-based process for the separation of mixtures of substances, which requires as small a membrane area as possible and yet still fulfills the required separation task and separation performance.
  • This task is solved by using a membrane cascade with decreasing separation temperature.
  • the invention therefore relates to a method for separating a mixture of substances using a membrane cascade comprising at least two stages, in which in each stage a substance separation takes place on at least one membrane at a Separation temperature occurs at which the respective separation temperature - seen in the direction of the inflowing mixture of substances - decreases from stage to stage.
  • the invention is based on the surprising finding that the area of a membrane cascade - and thus its requirement for separating membrane material - can be optimized while maintaining the required separation performance (rejection and volume flow of the feed to be processed) if the separation temperature within the cascade is lowered from stage to stage.
  • the invention teaches that the separation temperature within the cascade can be set specifically and separately for each individual stage, in such a way that the separation temperature decreases downstream from stage to stage.
  • the invention makes use of the observation that the rejection of the individual membrane separation stage depends on the separation temperature of this stage: In principle, the rejection of the membrane increases as the temperature decreases. As the rejection increases, the permeate flow also decreases, which in turn enables a smaller membrane area within this stage.
  • the total membrane area of a cascade can be optimized by setting the rejection relatively low in the first stage but increasing it from stage to stage by lowering the temperature. As a result, this means that the membranes become denser from stage to stage. The resulting decrease in the volume flow of the permeate can be used to reduce the overall membrane area.
  • membrane material refers to the material of the separation-active layer of a membrane.
  • membranes are preferably used which have a separation-active layer made of a material selected from cellulose acetate, cellulose triacetate, cellulose nitrate, regenerated cellulose, polyimides, polyamides, polyetheretherketones, sulfonated polyetheretherketones, aromatic polyamides, polyamideimides, polybenzimidazoles, polybenzimidazolones, polyacrylonitrile, polyarylethersulfones, polyesters, polycarbonates, polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, terminally or laterally organomodified siloxane, polydimethylsiloxane, silicones, polyphosphazenes, polyphenylsulfides, polybenzimidazoles, nylon-6,6, polysulfones, polyanilines, polyurethanes, acrylonitrile/glycidyl methacrylate (PANGMA)
  • the above-mentioned substances can be present in a cross-linked form, particularly in the separation-active layer, possibly by adding auxiliary substances, or as so-called mixed matrix membranes with fillers such as carbon nanotubes, metal organic frameworks or hollow spheres as well as particles of inorganic oxides or inorganic fibers, such as ceramic or glass fibers.
  • membranes which have a polymer layer of terminally or laterally organomodified siloxane, polydimethylsiloxane or polyimide as the active separation layer, which are made up of polymers with intrinsic microporosity (PIM) such as PIM-1, or where the active separation layer is made up of a hydrophobic ceramic membrane.
  • PIM intrinsic microporosity
  • membranes made of terminally or laterally organomodified siloxanes or polydimethylsiloxanes are commercially available.
  • the membranes can contain other materials.
  • the membranes can contain support or carrier materials onto which the separation-active layer is applied.
  • a selection of support materials describes EP0781166 , to which explicit reference is made.
  • a selection of commercially available solvent stable membranes are the MPF and Selro series from Koch Membrane Systems, Inc., various types from Solsep BV, the Starmem TM series from Grace/UOP, the DuraMem TM and PuraMem TM series from Evonik Industries AG, the Nano-Pro series from AMS Technologies, the HITK-T1 from IKTS, as well as oNF-1, oNF-2 and NC-1 from GMT Membrantechnik GmbH and the inopor ® nano types from Inopor GmbH.
  • membranes are also relevant for the separation performance of the individual stage:
  • the membrane is preferably designed as a spiral wound element
  • membranes can also be used in the form of plate modules, pillow modules, tube modules, hose modules, capillary modules, hollow fiber modules or membrane disks.
  • the connection of the stages within the cascade is also decisive for the required membrane area to fulfil the separation task:
  • the membrane cascade is preferably a reinforcement cascade, i.e. a connection arrangement in which the individual stages are connected in series in the direction of the permeate flow.
  • the inventive concept works particularly well with a reinforcement cascade because the connection is made in the direction of the decreasing permeate flow, which makes the optimization of the entire membrane area particularly successful.
  • the amplification cascade is designed in such a way that the resulting permeate has permeated all stages of the membrane cascade.
  • the retentate is then recycled into the feed of the same stage from which the retentate was recycled and/or into the feed of another stage located opposite to the direction of the incoming material mixture.
  • the recycled retentate is always mixed with a material stream with a lower degree of processing.
  • a membrane cascade must have at least two stages. However, a three- or four-stage membrane cascade can also be economical.
  • a membrane cascade is to be considered as isothermal, provided that no further technical measures are provided for temperature control within the membrane.
  • the naturally occurring heat losses within the cascade in the direction of the permeate are usually not sufficient to achieve optimal separation temperatures in the individual stages. For this reason, it is advisable to assign each stage of the A temperature control unit is assigned to the membrane cascade, which sets the temperature of the feed of the respective stage to the respective separation temperature assigned to the stage.
  • the temperature control unit does not necessarily have to be located inside the membrane cascade, but can also be located outside it. In particular, the mixture of substances to be separated can already be provided at the temperature required for the first stage.
  • the temperature control unit is, at its simplest, a cooler, since the temperature is lowered in the direction of the permeate flow.
  • the arrangement of a cooler within a membrane cascade naturally means that the membrane cascade has a thermal energy requirement in the form of cooling coolant.
  • the operating costs of a membrane cascade according to the invention can therefore be higher than those of a conventional membrane cascade that only consumes mechanical power. However, these higher operating costs can be offset by lower investment costs or improved retention and thus better product purity, so that the membrane cascade according to the invention is more economical than conventional systems despite its coolant requirement.
  • the process according to the invention involves the separation of homogeneously dissolved catalyst systems, as it has proven to be particularly cost-effective here.
  • the substance mixture originally comes from its homogeneously catalyzed chemical reaction and comprises at least one product of the reaction, at least one unreacted reactant of the reaction, and the catalyst system present in the reaction and/or at least one component and/or a degradation product thereof, wherein the catalyst system or its component or its degradation product is dissolved in the substance mixture.
  • the reaction is a hydroformylation.
  • the product is an aldehyde or an alcohol
  • the reactants are an olefin and synthesis gas.
  • the catalyst system is preferably a metal-organic complex of rhodium (although complexes of the other transition metals from groups 7-9 of the Periodic Table of the Elements can also be used), which can contain, for example, an organophosphorus compound as a ligand.
  • the process according to the invention could be used particularly advantageously in this specific field of application.
  • a membrane cascade is also disclosed which is intended for separating a substance mixture according to the invention.
  • the membrane cascade is designed in particular as a reinforcement cascade, comprising at least two stages arranged one behind the other, in which each stage is assigned a temperature control unit by means of which the temperature of the feed of the respective stage can be set to a respective separation temperature assigned to the stage, and in which the respective separation temperatures are set such that - viewed in the direction of the inflowing substance mixture - the respective separation temperature drops from stage to stage.
  • this membrane cascade for separating a dissolved catalyst complex and/or at least one component and/or a degradation product thereof from a mixture of substances originally originating from a chemical reaction homogeneously catalyzed in the presence of the catalyst complex.
  • the process according to the invention is preferably used for catalyst separation within homogeneously catalyzed industrial hydroformylation, a process for the hydroformylation of ethylenically unsaturated compounds by reaction with carbon monoxide and hydrogen in the presence of a catalyst system which contains a dissolved metal complex compound of a metal of the eighth subgroup of the Periodic Table of the Elements with at least one organophosphorus compound as ligand is also possible, in which a reaction mixture is obtained which, in addition to products of the hydroformylation, contains unreacted reactants and the catalyst system or at least components and/or degradation products thereof in solution, wherein the reaction mixture is fed to a catalyst separation in which the catalyst system or its components and/or degradation products are at least partially separated from the reaction mixture by means of membrane technology for the purpose of recycling to the hydroformylation, in which the catalyst separation comprises a membrane cascade having at least two stages, in which in each stage a substance separation takes place on at least one membrane at a separation temperature assigned to the respective stage, wherein -
  • FIG. 4 shows a first embodiment of the invention in the form of a two-stage amplification cascade which is suitable for carrying out a process according to the invention.
  • the feed F of the two-stage amplification cascade 30 is the output of a homogeneously catalyzed hydroformylation. More precisely, C 5 olefins (pentenes) are reacted with hydrogen and carbon monoxide in the presence of a rhodium phosphite catalyst system to form hexanals.
  • the reaction output is a mixture of the two hexanals formed (n-hexanal and 2-methylpentanal), in which the homogeneously dissolved catalyst is present in a concentration of 37 ppm (by mass).
  • the conversion of pentenes is 99% and the regioselectivity to the linear product is 67%.
  • the reaction output comprising the hexanals formed, unreacted pentenes, dissolved synthesis gas and the catalyst system are fed as feed F to the amplifier cascade 30. If necessary, the reaction output can be degassed beforehand, whereby a residual amount of synthesis gas must be retained in the feed in order to stabilize the organophosphorus ligand against deactivation.
  • the amplifier cascade 30 has two stages 31 and 32. Both stages 31, 32 are formed by two membrane modules connected in series, which are, however, to be regarded as a single membrane.
  • a silane-modified ceramic based on a ZrO2 carrier and a pore size of 3 nm is used as the membrane material, and tube modules of the type Inopor M07-19-41-L with a length of 40 inches and an area of 2.54m 2 were selected as the module design.
  • the special feature of the amplifier cascade 30 according to the invention is that a temperature control device 33, 34 assigned to the respective stage 31, 32 is provided in the feed of each membrane stage.
  • the temperature control devices 33, 34 are thermostatically controlled coolers which adjust the feed of the respective stages 31, 32 to a separation temperature assigned to the respective stage.
  • the separation temperatures of the stages are selected so that the separation temperature drops in the direction of the incoming feed F:
  • the first tempering device 33 sets the separation temperature of the first stage 31 to 43.4 °C; while the tempering device 34 of the second stage 32 sets the separation temperature of the second stage 32 to 30 °C.
  • the transmembrane pressure is set to 60 bar in each stage, for which a pump 35, 36 is provided in the feed of the respective stage.
  • the pump of the first stage 35 conveys the feed F through the first temperature control device 33 so that it reaches the first stage 31. There, a separation of substances takes place in such a way that the products and reactants contained in the reaction mixture overcome the membranes preferentially, i.e. more quickly, and accordingly accumulate in the permeate 37 of the first stage.
  • the catalyst system is not able to overcome the membrane so quickly, so that it accumulates in the retentate of the first stage, which is withdrawn from the membrane cascade 30 as the resulting retentate R and fed back into the hydroformylation reactor.
  • the permeate 37 of the first stage 31 also contains rhodium and organophosphorus ligand or its degradation products.
  • the permeate 37 of the first stage 31 is fed as feed to the second stage 32.
  • the pressure of the permeate 37 is increased again using the pump 36. Cooling then takes place in the temperature control device 34 so that membrane separation can take place again in the second stage 32 at the same pressure level but at a lower separation temperature.
  • the permeate from the second stage 32 is discharged from the two-stage amplification cascade 30 as the resulting permeate P. It is largely free of the catalyst system or any of its degradation products. It can now be fed to a distillative product separation in which the actual target product (hexanal) can be separated from high boilers formed in side reactions.
  • the retentate 38 of the second stage 32 is recycled within the membrane cascade 30, namely once via a return within the second stage 32, for which a return pump is arranged within the return 38, and via a second return 39, which recycles the retentate of the second stage 32 into the feed of the first stage 31.
  • the second return 39 does not require its own pump, since the pump 35 upstream of the first stage also sucks in the recycled retentate from the second stage 32.
  • the value RR int is set to 12.1 kmol/kmol in the second stage and to 10.5 kmol/kmol in the first stage. This means that (in terms of molar quantity) 12.1 or 10.5 times more is recirculated internally (eg stream 38) than is conveyed externally to the stage below (eg stream 39, or to the global retentate in the first stage).
  • the rejection of the first stage is lower than that of the second stage. In the first stage, the rejection is 88.7%, while the rejection in the second stage is 91.3%.
  • the permeate flow of the first stage 31 i.e. the volume flow of the permeate 37
  • the permeate flow of the second stage 32 i.e. the volume flow of the resulting permeate P. Accordingly, the membrane area of the first stage at 163 m2 is significantly larger than that of the second stage at 81.4 m2.
  • the two-stage membrane cascade 30 shown has a total membrane area of 244.4 m 2 . This results in a total rejection of 98.33% based on the catalyst complex. This means that 98.33% of the catalyst introduced with the feed can be recovered and leaves the membrane cascade 30 again via the resulting retentate R in the direction of the reactor. The remaining 1.67% of the catalyst system is lost with the permeate P.
  • a three-stage amplifier cascade is suitable for this purpose, as used for example in Figure 5 is shown.
  • the three-stage amplifier cascade 40 comprises three stages 41, 42, 43, which are analogous to the Figure 4 shown, two-stage amplifier cascade 30.
  • the resulting retentate R of the cascade 40 is fed by the first stage 41 withdrawn.
  • the resulting permeate P permeates all stages 41, 42 and 43.
  • the retentates from the second and third stages are recycled, partly into the feed of the same stage and partly into the feed of the previous stage.
  • the value RR int is 0.5 kmol/kmol in the first stage, 5.1 kmol/kmol in the second stage and 16.6 kmol/kmol in the third stage.
  • the membrane material used is uniform and the same as in Figure 4 shown two-stage amplifier cascade 30.
  • the identical transmembrane pressure of 60 bar was also selected.
  • the separation temperature decreases again in the direction of the permeate flow from 88.9 °C in the first stage 41, to 73.1 °C in the second stage 42, to 30.17 °C in the third stage 43.
  • the membrane area in the first stage was chosen to be 64.5 m 2 ; provided by two "Inopor M07-19-41-L" modules connected in series, each with a length of 40 inches and an area of 2.54 m 2 .
  • the second stage 42 has a membrane area of 61 m 2 , also realized via two membrane modules connected in series.
  • the membrane area was increased to 81.2 m 2 , provided by a single membrane.
  • the three-stage amplification cascade requires 206.7 m 2 of expensive membrane material.
  • its rejection based on the catalyst complex is 99.24 %.
  • the three-stage amplification cascade thus achieves better rejection with a smaller membrane area.
  • the Figure 5 The three-stage design shown is therefore significantly more effective than the one in Figure 4 shown two-stage membrane cascade.
  • FIG. 6 shows a corresponding four-stage amplifier cascade 50. Its connection is analogous to the three-stage amplifier cascade 40 and two-stage amplifier cascade 30.
  • the composition of the feed F and the membrane material and the module design correspond to the membrane cascades from the Figures 4 and 5 .
  • Levels 51, 52, 53 and 54 were chosen as follows: First level 51: Separation temperature 90 °C, transmembrane pressure 60 bar, number of membranes 2, membrane area 53.2 m2, RR int 0.3 kmol/kmol.
  • Second level 52 Separation temperature 85.5 °C, transmembrane pressure 60 bar, number of membranes 2, membrane area 73.9 m2, RR int 7.8 kmol/kmol.
  • Third level 53 Separation temperature 80.9 °C, transmembrane pressure 60 bar, number of membranes 2, membrane area 66.5 m2, RR int 4.8 kmol/kmol.
  • Fourth level 54 Separation temperature 63.9 °C, transmembrane pressure 60 bar, number of membranes 2 with a total area of 53.3 m2, RR int 6.1 kmol/kmol.
  • the four-stage membrane cascade 50 achieves a total rejection of 99.5 % with a total membrane area of 245.9 m 2 .
  • the membrane area is thus approximately the same size as that of the two-stage amplifier cascade 30 from Figure 4 , but the support is much better.
  • FIGS 7 and 8th show the effect of the temperature dependence of the retention or permeability used according to the invention.
  • Figures 7 and 8th show the results regarding catalyst rejection (Rh rejection) and permeability. The lower the temperature, the higher the rejection and the lower the permeability.
  • 1-pentene (68) was continuously fed to the reactor under oxygen exclusion in accordance with the reaction product removal via the permeate of the membrane separation stage.
  • the catalyst precursor was rhodium acetylacetonatodicarbonyl ( CAS No. 14847-82-9 ).
  • the ligand used was Alkanox P-24 ( CAS No. 26741-53-7 ) was used.
  • the rhodium concentration and the ligand concentration in the loop reactor were kept constant at 10 mg/kg and 1170 mg/kg respectively by continuous dosing.
  • the reaction was carried out under 50 bar synthesis gas pressure (CO/H 2 , mass ratio 1:1) at 110 °C.
  • the reaction product was continuously passed through a membrane separation stage (65) designed as a single-stage nanofiltration membrane.
  • the required transmembrane pressure is built up by the reactor pressure and a regulated permeate-side pressure.
  • the desired overflow of 500 kg/h over the high-pressure side of the membrane is set using the peripheral impeller pump (69).
  • a prototype of a membrane hydrophobized by silanization was installed as a monochannel tube from the Fraunhofer Institute for Ceramic Technologies and Systems IKTS.
  • the carrier consisted of Al 2 O 3 with an average pore size of 3 ⁇ m and a hydrophobized membrane layer based on a ZrO 2 layer with an average pore diameter of 3 nm.
  • the active membrane area is approximately 100 cm 2 .
  • the membrane was flowed over at 4.4 m/s. Temperatures on the membrane ranged from 30 to 90°C.
  • a synthesis gas pressure (CO/H 2 , mass ratio 1:1) of 10 bar was maintained on the permeate side, whereby a transmembrane pressure of 10 to 30 bar was set at a retentate side pressure of 20 to 40 bar.
  • permeate (66) which mainly consists of reaction product, was removed from the system via the membrane.
  • the catalyst and the ligand Alkanox were largely retained by the membrane and accumulated in the retentate (67).
  • the retentate (67) was continuously fed back into the jet loop reactor (61).
  • the process chain was evaluated using measurement and analysis data obtained by gas chromatography analysis, HPLC analysis, atomic absorption spectroscopy and optical emission spectrometry with inductively coupled high frequency plasma.
  • the reaction was investigated with regard to the conversion of 1-pentene as well as the yield and selectivity of aldehyde.
  • the membrane separation stage (65) was investigated with regard to permeate flow and rejection for rhodium.
  • the composition of the reaction output was as follows: 1-Penten 2-M.pentanal Hexanal rest 3.7% 53.3% 42.2% 0.8%

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  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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KR20160066045A (ko) 2013-12-16 2016-06-09 사빅 글로벌 테크놀러지스 비.브이. 자외선 및 열 처리된 중합 멤브레인들
DE102014209421A1 (de) 2014-05-19 2015-11-19 Evonik Degussa Gmbh Membrangestützte Katalysatorabtrennung bei der Epoxidierung von cyclischen, ungesättigten C12-Verbindungen zum Beispiel Cyclododecen (CDEN)
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CN105579118A (zh) 2016-05-11
TW201515690A (zh) 2015-05-01
DE102013215004A1 (de) 2015-02-05
MY185596A (en) 2021-05-24
KR20160036616A (ko) 2016-04-04
US20160158703A1 (en) 2016-06-09
US9713791B2 (en) 2017-07-25
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JP2016528223A (ja) 2016-09-15
CN105579118B (zh) 2018-07-20

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